[ring-14C]-2,4,6-trinitrotoluene | 164534-18-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [ring-14C]-2,4,6-trinitrotoluene
• 英文别名: 2,4,6-trinitrotoluene；14C-TNT-ring；2-methyl-1,3,5-trinitro(1,2,3,4,5,6-14C6)cyclohexa-1,3,5-triene
• CAS: 164534-18-3
• 化学式: C₇H₅N₃O₆
• 分子量: 239.067
• InChiKey: SPSSULHKWOKEEL-POOLIRAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  138
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,4,6-三硝基甲苯 、 [ring-14C]-2,4,6-trinitrotoluene 在 Clostridium acetobutylicum 、 氢气 作用下， 以 甲醇 、 水 为溶剂， 反应 24.0h， 以75%的产率得到4-羟基氨基-2,6-二硝基甲苯
  参考文献：
  名称：

  Bamberger Rearrangement during TNT Metabolism by Clostridium acetobutylicum

  摘要：

  Studies were conducted to isolate and identify polar and oxygen-sensitive intermediates of 2,4,6-trinitrotoluene (TNT) transformation by Clostridium acetobutylicum. Studies conducted in anaerobic cell extracts demonstrated that a polar product formed from the transformation of 2,4-dihydroxylamino-6-nitrotoluene by a mechanism known as the Bamberger rearrangement. The product was stabilized by derivatization with acetic anhydride, and the structure was confirmed by mass spectroscopy, (1)H NMR, and IR spectroscopy techniques. The reaction occurred in the presence of cell extract and H(2) but did not occur in cell extract-free controls. From spectroscopic data, the product of 2,4-dihydroxylamino-6-nitrotoluene rearrangement was identified as either 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) or 2-hydroxylamino-4-amino-5-hydroxyl-6-nitrotoluene (6-amino-4-hydroxylamino-3-methyl-2-nitrophenol). Acid-catalyzed rearrangement of 2,4-dihydroxylamino-6-nitrotoluene resulted in a single product, which after derivatization, was identical to a derivatized product from cell extracts. Acid-catalyzed Bamberger rearrangement occurs with the hydroxyl addition para to the participating hydroxylamine, indicating that the 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) was the product isolated form cell extracts. This product was also confirmed in whole cell systems that had been fed TNT. Following derivatization of the culture broth, a product was isolated that was identical to hose isolated from crude cell extracts and acid catalysis experiments.

  DOI：

  10.1021/es970612s
• 作为产物：
  描述：

  [ring-UL-(14)C]toluene 在 硫酸 、 硝酸 作用下， 以61%的产率得到[ring-14C]-2,4,6-trinitrotoluene
  参考文献：
  名称：

  Synthesis of 14C-labelled hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), nitrocellulose (NC) and glycidylazide polymer (GAP) for use in assessing the biodegradation potential of these energetic compounds

  摘要：

  在受高能化合物污染的土壤生物修复研发项目的框架内，研究人员正在研究高能产品（如六亚甲基三硝胺（RDX）、三硝基甲苯（TNT）、硝化纤维素（NC）和缩水甘油叠氮聚合物（GAP））的生物降解。为了跟踪生物降解过程，必须使用放射性碳-14标记产品进行微环境测定。14C-RDX是通过根据Hale工艺对六亚甲基四胺（HMTA）进行硝化制备的。14C-环和甲基标记的TNT是根据Dorey和Carper程序合成的。14C-纤维素是由乙酰木糖杆菌从14C-葡萄糖合成的。14C-纤维素的硝化反应产生了14C-硝化纤维素。14C-缩水甘油叠氮聚合物是通过14C-环氧氯丙烷（ECH）的聚合和叠氮化合成的，而14C-环氧氯丙烷是由14C-甘油合成的。14C-甘油的氢氯化反应和所得14C-1,3-二氯-2-丙醇的环氧化反应产生了14C-环氧氯丙烷。本文描述了这些14C标记炸药的合成方法。

  DOI：

  10.1002/jlcr.2580360608

文献信息

• Microbiotic synthesis of¹⁴C-ringlabelled aminodinitrotoluenes (ADNT) and diaminonitrotoluenes (DANT)
  作者：Mario Kröger、Gregor Fels

  DOI：10.1002/jlcr.556

  日期：2002.3.15

  The four 14C-ringlabelled TNT-metabolites 2-aminodinitrotoluene (2-ADNT), 4-aminodinitrotoluene (4-ADNT), 2,4-diaminonitrotoluene (2,4-DANT) and 2,6-diaminonitrotoluene (2,6-DANT) were synthesized in one step from TNT by reduction with baker's yeast (Saccharomyces cervisiae). Copyright © 2002 John Wiley & Sons, Ltd.

  用面包酵母（Saccharomyces cervisiae）还原 TNT，一步合成了四种 14C 标记的 TNT 代谢物：2-氨基二硝基甲苯（2-ADNT）、4-氨基二硝基甲苯（4-ADNT）、2,4-二氨基二硝基甲苯（2,4-DANT）和 2,6-二氨基二硝基甲苯（2,6-DANT）。Copyright © 2002 John Wiley & Sons, Ltd. All Rights Reserved.
• Synthesis of 14C-labelled hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), nitrocellulose (NC) and glycidylazide polymer (GAP) for use in assessing the biodegradation potential of these energetic compounds
  作者：Guy Ampleman、Sonia Thiboutot、J. Lavigne、A. Marois、J. Hawari、A. M. Jones、D. Rho

  DOI：10.1002/jlcr.2580360608

  日期：1995.6

  Within the framework of an R & D project on bioremediation of soils contaminated with energetic compounds, the biodegradation of energetic products such as hexogen (RDX), trinitrotoluene (TNT), nitrocellulose (NC) and glycidyl azide polymer (GAP) is under study. Microcosm assays must be performed with radioactive carbon-14 labelled products in order to follow the biodegradation process. 14C-RDX was prepared by nitration of hexamethylenetetramine (HMTA) according to the Hale process. 14C-ring and methyl labelled TNTs were synthesized according to the Dorey and Carper procedure. 14C-cellulose was synthesized from 14C-glucose by Acetobacter xylinum. Nitration of the 14C-cellulose yielded 14C-nitrocellulose. 14C-glycidyl azide polymer was obtained by polymerization and azidation of 14C-epichlorohydrin (ECH) which was synthesized from 14C-glycerol. Hydrochlorination of 14C-glycerol and epoxidation of the resulting 14C-1,3-dichloro 2-propanol yielded 14C-ECH. The syntheses of these 14C-labelled explosives are described in this paper.

  在受高能化合物污染的土壤生物修复研发项目的框架内，研究人员正在研究高能产品（如六亚甲基三硝胺（RDX）、三硝基甲苯（TNT）、硝化纤维素（NC）和缩水甘油叠氮聚合物（GAP））的生物降解。为了跟踪生物降解过程，必须使用放射性碳-14标记产品进行微环境测定。14C-RDX是通过根据Hale工艺对六亚甲基四胺（HMTA）进行硝化制备的。14C-环和甲基标记的TNT是根据Dorey和Carper程序合成的。14C-纤维素是由乙酰木糖杆菌从14C-葡萄糖合成的。14C-纤维素的硝化反应产生了14C-硝化纤维素。14C-缩水甘油叠氮聚合物是通过14C-环氧氯丙烷（ECH）的聚合和叠氮化合成的，而14C-环氧氯丙烷是由14C-甘油合成的。14C-甘油的氢氯化反应和所得14C-1,3-二氯-2-丙醇的环氧化反应产生了14C-环氧氯丙烷。本文描述了这些14C标记炸药的合成方法。
• 14C-TNT synthesis revisited
  作者：Mario Kr�ger、Gregor Fels

  DOI：10.1002/(sici)1099-1344(20000315)43:3<217::aid-jlcr305>3.0.co;2-u

  日期：2000.3.15

  Mineralization experiments requiring the synthesis of substantial amounts of [ring-C-14]trinitrotoluene, led us to reinvestigate die published procedures for labeled TNT. Here we describe an efficient, economical and reproducible procedure that results in crystalline C-14-TNT in 83 % yield with chemical and radiochemical purity of > 99 %. Determination of the specific activity (1.12 GBq/mmol) by mass spectrometry disclosed that the radioactive TNT molecules exhibit an uneven distribution of four to six aromatic C-14-atoms.
• Bamberger Rearrangement during TNT Metabolism by <i>Clostridium acetobutylicum</i>
  作者：J. B. Hughes、C. Wang、K. Yesland、A. Richardson、R. Bhadra、G. Bennett、F. Rudolph

  DOI：10.1021/es970612s

  日期：1998.2.1

  Studies were conducted to isolate and identify polar and oxygen-sensitive intermediates of 2,4,6-trinitrotoluene (TNT) transformation by Clostridium acetobutylicum. Studies conducted in anaerobic cell extracts demonstrated that a polar product formed from the transformation of 2,4-dihydroxylamino-6-nitrotoluene by a mechanism known as the Bamberger rearrangement. The product was stabilized by derivatization with acetic anhydride, and the structure was confirmed by mass spectroscopy, (1)H NMR, and IR spectroscopy techniques. The reaction occurred in the presence of cell extract and H(2) but did not occur in cell extract-free controls. From spectroscopic data, the product of 2,4-dihydroxylamino-6-nitrotoluene rearrangement was identified as either 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) or 2-hydroxylamino-4-amino-5-hydroxyl-6-nitrotoluene (6-amino-4-hydroxylamino-3-methyl-2-nitrophenol). Acid-catalyzed rearrangement of 2,4-dihydroxylamino-6-nitrotoluene resulted in a single product, which after derivatization, was identical to a derivatized product from cell extracts. Acid-catalyzed Bamberger rearrangement occurs with the hydroxyl addition para to the participating hydroxylamine, indicating that the 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) was the product isolated form cell extracts. This product was also confirmed in whole cell systems that had been fed TNT. Following derivatization of the culture broth, a product was isolated that was identical to hose isolated from crude cell extracts and acid catalysis experiments.